JP2006167110A - Medical apparatus - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a seal member and a medical apparatus provided with stable slidability without imparting lubricants to a slide surface and capable of maintaining sealability inside a medicine housing space. <P>SOLUTION: The seal member 1 can be liquid-tightly and airtightly slid on the inner surface 42 of a space capable of housing medicine in the medical apparatus 10 capable of housing the medicine 26, and comprises a core part 2 and a coating layer 3 provided on a part to be in contact with the inner surface of the core part 2. The coating layer 3 is composed of a coating formed of a composition containing slidability imparting components and flexibility imparting components and particulates held by the coating, and the coating layer 3 has a rough surface due to particulates. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a medical device having stable slidability and a medical device including a medical member having stable slidability.

Conventionally, syringe gaskets for prefilled syringes pre-filled with chemicals are lubricated with silicone oil such as polysiloxane on the sliding parts such as the outer surface of the gaskets in order to increase the slidability of the gaskets and discharge the chemicals stably. It is necessary to apply as an agent. However, some chemical solutions are difficult to be prefilled syringes due to the interaction with the lubricant. For example, it is known that monoammonium glycyrrhizinate, which is one of injections, may generate insoluble foreign matter when it comes into contact with silicone oil.
The method of improving the slidability by applying the lubricant to the sliding portion of the gasket as described above is frequently used in disposable injection devices and the like, but in prefilled syringes and the like that store the drug for a long time, the stored drug is used. In consideration of the influence on the above, a lubricant is not applied.

  In order to solve the above problems, Japanese Patent Application Laid-Open No. 2001-104480 (Patent Document 1) (“Rubber Piston Used for Sealing a Plastic Prefilled Syringe”), and the present applicant, The gasket shown to -89717 gazette (patent document 2) is proposed. This gasket is a gasket formed by coating at least the outer periphery of the gasket body with a fluororesin film made of a material having a lower coefficient of friction than the gasket body material, and the surface roughness of the surface on the outer cylinder side of the resin film. Is Ra1, and the surface roughness of the surface of the resin film on the gasket body side is Ra2, the relationship of 1.5Ra1 ≦ Ra2 is satisfied, and the surface roughness Ra1 is 0.1 to 1.5 μm. It is said that it is preferable.

JP 2001-104480 A JP 2002-89717 A

The above-mentioned gasket is considered to exert a sufficient effect depending on the use conditions, but when containing an injection solution containing a component having surface activity as a content solution, or when administering under high pressure, etc. Even when the gasket is exposed to harsh conditions, the basic performance of the gasket, which prevents liquid leakage, is maintained, and stable and high slidability is achieved without using a lubricant such as silicone oil. What you have is needed.
Further, a highly fine and stable discharge performance, for example, a prefilled syringe preparation used in a syringe pump or the like, which has a stable and high slidability, is required to have a higher function. That is, when the chemical solution is discharged under extremely low speed conditions that cannot be visually confirmed (for example, in a syringe with a diameter of about 24 mm, the moving speed when discharged at 1 mL / hour is about 2 mm / hour) In some cases, a discharge state called “Frequency” may occur, which may hinder accurate administration of the drug solution.
Therefore, the present invention solves the above-described problems, and includes a medical device having a stable sliding property and a medical member having a stable sliding property without applying a lubricant to the sliding surface. Tools are provided.

What achieves the above object is as follows.
(1) A medical device that is slidably in contact with a medical member, the medical device including a coating layer provided in a portion that contacts the medical member, and the coating layer imparts slidability. And a coating layer formed of a composition containing a component and a flexibility-imparting component; and fine particles held in the coating; and the coating layer has a rough surface caused by the fine particles. Medical tools.
(2) The medical device according to (1), wherein the slidability imparting component is a fluorine-based resin and a silicon-based resin.
(3) The medical device according to (1) or (2), wherein the flexibility-imparting component is a urethane resin.

Moreover, what achieves the said objective is as follows.
(4) A medical device that slidably contacts a medical member, the medical device including a coating layer provided on a portion that contacts the medical member, the coating layer including a fluororesin, It consists of a film formed of a composition containing a silicon-based resin and a urethane-based resin and fine particles held in the film, and the coating layer has a rough surface caused by the fine particles. Medical tools.
(5) The medical device according to any one of (1) to (4), wherein the medical device is made of an elastic material.
(6) The medical device according to any one of (1) to (4), wherein the medical device is slidably housed inside a medical member.
(7) The medical device according to (6), wherein the medical member is a syringe outer cylinder, and the medical device is a syringe gasket.
(8) The medical device according to (7), wherein the covering layer also covers an outer surface portion of the syringe gasket that defines a space together with an inner surface of the syringe outer cylinder.
(9) The medical device according to any one of (1) to (8), wherein the coating layer covers only a portion of the medical device that contacts the medical member.

Moreover, what achieves the said objective is as follows.
(10) A medical device including a first medical member and a second medical member slidably in contact with the first medical member, wherein the first medical member includes the first medical member, A coating layer provided on a portion in contact with the second medical member, the coating layer being held by the coating film formed by the composition containing the slidability imparting component and the flexibility imparting component; A medical device having a rough surface caused by the fine particles.
(11) The medical device according to (10), wherein the slidability imparting component is a fluorine-based resin and a silicon-based resin.
(12) The medical device according to (10) or (11), wherein the flexibility-imparting component is a urethane resin.

Moreover, what achieves the said objective is as follows.
(13) A medical device including a first medical member and a second medical member slidably in contact with the first medical member, wherein the first medical member includes the first medical member, A coating layer provided on a portion in contact with the second medical member is provided, and the coating layer is held by the coating film formed of a composition containing a fluorine resin, a silicon resin, and a urethane resin, and the coating film. A medical device comprising a fine particle, and the coating layer has a rough surface caused by the fine particle.
(14) The medical device according to any one of (10) to (13), wherein the first medical member is made of an elastic material.
(15) The medical device according to any one of (10) to (14), wherein the first medical member is slidably housed inside a second medical member.
(16) The medical device according to (15), wherein the medical device is a syringe, the first medical member is a gasket, and the second medical member is an outer cylinder.
(17) The medical device according to (16), wherein the medical device is a prefilled syringe.
(18) The medical device according to any one of (10) to (17), wherein the coating layer covers only a portion of the first medical member that comes into contact with the second medical member.
(19) The urethane resin or silicon resin or a mixture thereof constituting the coating layer is any one of the above (2) to (9) or (11) to (18), which functions as a binder. Medical tools.
(20) At least one of the fluororesin, the silicon resin, and the urethane resin is a thermosetting resin according to any one of (2) to (9) or (11) to (19). Medical tools.
(21) The medical device according to any one of (2) to (9) or (11) to (20), wherein the fluororesin has polytetrafluoroethylene or polytetrafluoroethylene in a basic structure. .
(22) The medical device according to any one of (2) to (9) or (11) to (21), wherein the silicon-based resin has polysiloxane in a basic structure.
(23) The medical device according to any one of (3) to (9) or (12) to (22), wherein the urethane-based resin has polyurethane as a basic structure.

(24) The medical device according to any one of (1) to (23), wherein the coating layer has a thickness of 1 to 20 μm.
(25) The medical device according to any one of (1) to (24), wherein the composition forming the film contains a silane coupling agent cured product.
(26) The medical device according to any one of (1) to (25), wherein the fine particles are at least one selected from the group consisting of synthetic resin fine particles and inorganic fine particles.
(27) The synthetic resin fine particles are at least selected from the group consisting of silicone resin fine particles, styrene resin fine particles, olefin resin fine particles, polyvinyl acetate fine particles, polyester fine particles, polyamide fine particles, polymethacrylate fine particles, and fluororesin fine particles. The medical device according to (26), which is a kind.
(28) The medical device according to (26), wherein the inorganic fine particles are at least one selected from the group consisting of ceramic fine particles, talc fine particles, and metal oxide fine particles.
(29) The medical device according to (28), wherein the ceramic fine particles are at least one selected from the group consisting of silica fine particles, alumina fine particles, zirconia fine particles, and zeolite fine particles.
(30) The medical device according to (28), wherein the metal oxide fine particles are at least one selected from the group consisting of titanium oxide fine particles and zinc oxide fine particles.

The medical device of the present invention is a medical device that slidably contacts a medical member, and the medical device includes a coating layer provided in a portion that contacts the medical member, and the coating layer includes: The coating layer is formed of a composition containing a slidability-imparting component and a flexibility-imparting component, and fine particles held in the coating, and the coating layer has a rough surface caused by the fine particles. It has become. For this reason, the medical device has liquid-tightness and stable slidability without applying a lubricant to the sliding surface.
In addition, the medical device of the present invention is a medical device that is stored in a liquid-tight and slidable manner inside a medical member, and the medical device is provided with a coating layer provided in a portion that comes into contact with the medical member. The coating layer is composed of a coating formed of a composition containing a fluorine-based resin, a silicon-based resin, and a urethane-based resin, and fine particles held in the coating, and the coating layer is It has a rough surface due to the fine particles. For this reason, the medical device has liquid-tightness and stable slidability without applying a lubricant to the sliding surface.

The medical device of the present invention is a medical device comprising a first medical member and a second medical member slidably in contact with the first medical member, wherein the first medical member is the first medical member. The medical member includes a coating layer provided at a portion in contact with the second medical member, and the coating layer is a film formed of a composition containing a slidability imparting component and a flexibility imparting component. And the fine particles held in the coating, and the coating layer has a rough surface caused by the fine particles. For this reason, the first medical member has liquid-tightness and has stable slidability without applying a lubricant to the sliding surface.
Moreover, the medical device of this invention is a medical device provided with the 1st medical member and the 2nd medical member which accommodates this 1st medical member inside so that liquid-tight sliding is possible. A coating layer provided on a portion of the first medical member in contact with the second medical member, wherein the coating layer contains a fluorine-based resin, a silicon-based resin, and a urethane-based resin. And the coating layer has a rough surface caused by the fine particles. For this reason, the first medical member has liquid-tightness and has stable slidability without applying a lubricant to the sliding surface.

A medical device that is an embodiment of the present invention will be described.
1 is a front view of an embodiment in which the medical device of the present invention is applied to a syringe gasket, FIG. 2 is a cross-sectional view of the syringe gasket shown in FIG. 1, and FIG. 3 is a plan view of the syringe gasket shown in FIG. 4 and 4 are bottom views of the syringe gasket shown in FIG.
The medical device 1 of the present invention is a medical device that is slidably in contact with a medical member, and includes a coating layer 3 provided in a portion that contacts the medical member. The coating layer 3 is composed of a coating formed of a composition containing a mobility-imparting component and a flexibility-imparting component, and fine particles held in the coating, and the coating layer 3 has a rough surface caused by the fine particles. Yes.
The medical device 1 of the present invention is a medical device that is stored in a liquid-tight and slidable manner inside a medical member, and includes a coating layer 3 provided on a portion that comes into contact with the medical member. And the coating layer 3 consists of the film formed with the composition containing a fluorine-type resin, a silicon-type resin, and a urethane-type resin, and the microparticles | fine-particles hold | maintained at the film, and the coating layer 3 is a microparticle. The resulting rough surface is the surface.

The medical device 10 of the present invention is a medical device including a first medical member 1 and a second medical member 11 slidably in contact with the first medical member. The member includes a coating layer 3 provided in a portion in contact with the second medical member, and the coating layer 3 includes a coating film and a coating film formed of a composition containing a slidability imparting component and a flexibility imparting component. The coating layer 3 has a rough surface caused by the fine particles.
The medical device 10 according to the present invention is a medical device including the first medical member 1 and the second medical member 11 slidably in contact with the first medical member 1. A coating layer 3 provided on a portion of the medical member 1 in contact with the second medical member 11, and the coating layer 3 contains a fluorine-based resin, a silicon-based resin, and a urethane-based resin. And the coating layer 3 has a rough surface caused by the fine particles.

The medical device of this invention is demonstrated using the Example applied to the gasket and syringe for syringes.
The medical device 1 of this embodiment is a syringe gasket 1 that is stored in a liquid-tight and slidable manner inside a syringe outer cylinder 11 that is a medical member. Moreover, the gasket 1 is provided with the coating layer 3 provided in the part which contacts the outer cylinder 11, and the coating layer 3 is formed with the composition containing a fluorine resin, a silicon resin, and a urethane resin. The coating layer is composed of fine particles held by the coating layer, and the coating layer has a rough surface caused by the fine particles. The gasket 1 includes a core portion 2 and a coating layer 3 provided at least on the outer surface of the core portion 2 and in contact with the inner surface of the outer cylinder. The covering layer 3 may be provided on the entire outer surface of the core portion 2.
Moreover, the medical device 10 of this embodiment is a syringe 10, a syringe gasket 1 as a first medical member, and a second medical member that houses the gasket 1 in a liquid-tight slidable manner. And a covering layer 3 provided on a portion of the gasket 1 in contact with the outer cylinder 11, and the covering layer 3 is made of fluorine resin, silicon resin and urethane resin. It contains. When the coating layer 3 is provided on the gasket 1, the coating layer 3 is provided at least on the outer surface of the core portion 2 of the gasket 1 and in contact with the inner surface of the outer cylinder 11. In addition, you may provide the coating layer 3 in the whole outer surface of the core part 2 of the gasket 1. FIG. Further, when the coating layer is provided on the inner surface of the outer cylinder 11, it is provided on the inner surface of the portion that becomes the sliding region of the gasket 1.

Then, the gasket and syringe which are the Example of the medical device of this invention are demonstrated.
As shown in FIGS. 1, 2, and 5, the core portion 2 of the syringe gasket 1 has a main body portion 5 extending to substantially the same outer diameter and a tapered shape provided on the front end side of the main body portion 5 toward the front end side. A taper portion 6 that is reduced in diameter, a plunger mounting portion 4 provided inside from the base end of the main body portion 5 toward the front end side, and a front end side annular rib 7a provided on a side surface of the front end portion of the main body portion 5. The rear end side annular rib 7b provided on the rear end side surface of the main body 5 is provided.
As shown in FIGS. 2 and 4, the plunger mounting portion 4 is a substantially cylindrical concave portion extending from the base end to the vicinity of the distal end portion inside the main body portion 5. A threaded portion 8 that can be threadedly engaged with a threaded portion formed in the portion is provided. The front end surface of the recess is formed substantially flat. Note that the plunger mounting portion is not limited to the screwing portion, and may be an engaging portion that engages with the distal end portion of the plunger.
Since the distal end side annular ribs 7a and 7b are made slightly larger than the inner diameter of the outer cylinder 11 for syringes, they are compressed and deformed in the outer cylinder 11. In the embodiment, two annular ribs are provided, but three or more annular ribs may be provided.

  The constituent material of the core part 2 is preferably an elastic material. Elastic materials include natural rubber, isoprene rubber, butyl rubber, chloroprene rubber, nitrile-butadiene rubber, styrene-butadiene rubber, silicone rubber and other rubber materials (especially those vulcanized), styrene elastomers, hydrogenated Styrenic elastomers, and these styrenic elastomers mixed with polyolefins such as polyethylene, polypropylene, polybutene, and α-olefin copolymers, and oils such as liquid paraffin and process oil, and inorganic powders such as talc, cast, and mica Is mentioned. Furthermore, polyvinyl chloride elastomers, olefin elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers, and mixtures thereof can be used as constituent materials. As the constituent material, diene rubbers and styrene elastomers are particularly preferable from the viewpoints of elastic properties, steam pressure sterilization resistance, and the like.

The coating layer 3 should just be provided in the cyclic | annular rib part at least. Specifically, the coating layer 3 should just be provided in the front end side annular rib 7a and the base end side annular rib 7b part.
The thickness of the coating layer 3 is preferably 1 to 20 μm, particularly preferably 3 to 10 μm. If it is 1 μm or more, sufficient sliding performance is exhibited, and if it is 10 μm or less, the elasticity of the gasket is not affected, and the rough surface caused by the fine particles can be surely expressed.
The coating layer 3 is composed of a film formed of a composition containing a slidability-imparting component and a flexibility-imparting component, and fine particles held in the film. As the slidability imparting component, a fluorine-based resin and a silicon-based resin are preferable. As the flexibility-imparting component, a urethane-based resin is preferable.

In other words, the coating layer 3 is composed of a film formed of a composition containing a fluorine resin, a silicon resin, and a urethane resin, and fine particles held in the film. In particular, the coating is preferably formed of a mixture of a fluorine-based resin, a silicon-based resin, and a urethane-based resin. As fluorine-based resin, silicon-based resin, and urethane-based resin, any solvent-based solvent dissolved in an organic solvent and water-based emulsified or dispersed water can be applied. From the viewpoint of suitability, water-based ones are preferable. Furthermore, it is preferable that the composition which forms a film contains the silane coupling agent hardened | cured material. By doing in this way, film formation is performed rapidly.
In this way, the coating, which is the surface portion of the coating layer, contains a slidability imparting component and a flexibility imparting component, ensuring high liquid-tightness because the physical properties of the core portion to be maintained are not impaired. In addition, the coating layer has higher slidability on the rough surface formed by the contained fine particles.

Examples of the fluororesin used as one of the coating materials in the coating layer include polytetrafluoroethylene (PTFE), tetrafluoroethylene (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether (PFA), polychlorotrifluoro Ethylene (PCTFE), polyvinylidene fluoride (PVDF), etc. are mentioned, in particular, a PTFE derivative having tetrafluoroethylene in the basic structure, which can be uniformly dissolved, dispersed and suspended in an aqueous solvent, Further, those that exhibit organic solvent resistance, water resistance, acid resistance, and alkali resistance by thermosetting are preferred, and those that have safety and durability when used in medical rubber stoppers are more preferred.
Furthermore, as the fluororesin, a so-called aqueous fluororesin is preferable. Examples of aqueous fluororesins include fluoroolefins such as tetrafluoroethylene and trifluorochloroethylene, vinyl fluoride, vinylidene fluoride, hexafluoroisobutylene, perfluoro (meth) acrylic acid or alkyl esters thereof, and (meth) acrylic acid. A copolymer of a fluorine-containing monomer such as fluoroalkyl ester, perfluorovinyl ether, and perfluoroalkyl vinyl ether with cyclohexyl vinyl ether, alkyl vinyl ether, hydroxyalkyl vinyl ether, aliphatic carboxylic acid vinyl ester, hydroxyalkyl vinyl ester, What melt | dissolved, disperse | distributed and emulsified in the medium is mentioned. In particular, the fluororesin is preferably a hydrophilic resin having tetrafluoroethylene as a basic structure. By adding such a fluororesin to the resin for forming the coating layer 3, high lubricity is imparted to the gasket surface. In addition, since the fluororesin is very rarely modified by chemicals, it is suitable for use in a medical rubber stopper.

The silicon-based resin used as one of the film forming materials can be easily and uniformly dispersed and suspended in an aqueous solvent, and further heat-cured to provide resistance to organic solvents, water resistance, What shows acid resistance and alkali resistance is preferable. Further, as the silicon-based resin, those having safety and durability when used for medical rubber stoppers are used. By adding such a silicon-based resin to the resin for forming the coating layer 3, sticking at the contact portion between the gasket surface and the inner surface of the outer cylinder is reduced, and the initial sliding resistance is reduced. The basic structure of the silicon-based resin is the same as that used for medical silicone oil. Furthermore, the silicon resin in the coating layer is extracted with an organic solvent such as hexane and methyl butyl ketone, and the silicon-based resin-derived substance is measured by a conventional measuring method such as an emission analyzer. However, it is preferable that the silicon-based resin-derived substance is not detected.
The silicon-based resin to be used is a hydrophilic resin having a polysiloxane as a basic structure, and a so-called aqueous silicon resin, in other words, an aqueous silicone compound is preferable. Moreover, as a silicon-type resin, what has a film formation property is preferable.

As the silicon resin (silicone compound), various types can be used. For example, an alkoxysilane group, an organosiloxane compound, or a polysiloxane composed of a condensate thereof dispersed, emulsified and dissolved in an aqueous medium, and further an alkoxysilyl group A copolymer emulsion obtained by copolymerizing the containing vinyl monomer with another vinyl monomer as required, or an emulsion obtained by combining polysiloxane with an organic polymer can also be used.
Specific examples of the silicon resin include methyltrimethoxysilane, methyltriethoxysilane, methyltriisobutoxysilane, methyltributoxysilane, methyl sec-trioctyloxysilane, methyltriphenoxysilane, and phenyltrimethoxysilane. , Phenyltriethoxysilane, methyltri (acryloyloxyethoxy) silane, methyltri (glycidyloxy) silane, octyltriethoxysilane, lauryltriethoxysilane, stearyltrimethoxysilane, silane compounds of stearyltriethoxysilane, or their condensation The thing which disperse | distributed, emulsified, and melt | dissolved the thing in the aqueous medium is mentioned.
Furthermore, as the aqueous silicon-based resin, a polysiloxane composite aqueous emulsion having a core part which is a crosslinked polymer and a shell part which is a non-crosslinked polymer covering the core part, and a polysiloxane in the vicinity of the surface of the shell is suitable. Can be used for By using such a thing, the film forming property of the coating layer 3 formed, denseness, and durability become high.

As the urethane resin used as one of the materials for forming the film, a hydrophilic resin having a polyurethane as a basic structure is preferable. The polyurethane is preferably one that can be easily and uniformly dispersed and suspended in an aqueous solvent. Further, as the urethane resin, those having safety and durability required for a medical rubber stopper are used by further curing (for example, thermosetting). This urethane-based resin alone did not give any effect on gasket sliding performance such as lubricity, but by blending with the above-mentioned fluorine-based resin and silicon-based resin, even at ultra-low speed sliding There was an effect of greatly improving and maintaining stable operation. Moreover, since it has the property which is excellent in adhesiveness with the gasket base-material surface, and is rich in a softness | flexibility, it is considered that the deterioration inhibitory effect of the film of the coating layer 3 formed is exhibited.
As the urethane resin used, a so-called aqueous urethane resin is preferable.
The aqueous urethane resin may be either a urethane dispersion obtained by emulsifying or dispersing a urethane resin in an aqueous solvent, or a water-soluble polyurethane resin.
Examples of urethane dispersions include, for example, polyol components such as (poly) ethylene glycol, (poly) tetramethylene glycol and polycarbonate diol, hydrophilic components such as 2,2-dimethylolpropionic acid, tolylene diisocyanate, hexa There are self-emulsifying aqueous urethane dispersions obtained by polymerizing polyisocyanate compounds such as methylene diisocyanate and isophorone diisocyanate. Moreover, as water-soluble polyurethane-type resin, there exists what has carboxylic acid and / or carboxylate salt couple | bonded together in the chain | strand of polyurethane-type resin. Such a product can be obtained, for example, by adding a diol having a carboxylic acid group to a diol and a diisocyanate, and polymerizing (neutralizing the carboxylic acid group if necessary) in the production of a polyurethane resin. By introducing a carboxylic acid group in this way, an aqueous polyurethane resin having a water dispersion type or water solubility is obtained. Moreover, you may make it aqueous by adding an emulsifier as needed.
In general, the polyurethane resin preferably has a number average molecular weight of about 1,000 or more, particularly about 10,000 or more, and substantially no free isocyanate groups remain in the molecule. Is desirable.

  And when using the above water-based fluororesins, water-based silicon resins, and water-based urethane resins, water (which may contain alcohol) is used as a solvent. A coating solution can be prepared, and if necessary, it can be easily diluted with water (which may contain an alcohol). And the coating liquid produced can be applied to the gasket, dried, and further heated if necessary to form a coating layer. Since the coating liquid uses water as a solvent, the solvent does not denature the gasket-forming material, and the environment does not deteriorate due to volatilization during operation. The content of fluorine resin, silicon resin and urethane resin in the coating liquid is 0.1 to 10% by weight for fluorine resin, 1 to 30% by weight for silicon resin, and 1 to 10 for urethane resin. It is preferable that it is weight%. The weight ratio of the fluorine-based resin, the silicon-based resin, and the urethane-based resin in the coating layer 3 to be formed is such that the fluorine-based resin: silicon-based resin: urethane-based resin is 0.1 to 10: 1 to 30: 1. 10 is preferable.

Furthermore, the coating layer 3 contains a large number of fine particles held by the coating. The coating layer 3 has a rough surface due to the contained fine particles. By being such a rough surface, the coating layer 3 provides more stable slidability.
The degree of the rough surface, in other words, the surface roughness (Ra, measurement method JISB0601: 1994) is preferably 1.7 to 4.5 μm, and particularly preferably 2.0 to 3.0 μm. It can be said that the surface roughness Ra1 of Patent Document 2 (Japanese Patent Laid-Open No. 2002-89717) has a sufficiently high roughness compared to 0.1 to 1.5 μm.
The fine particles are preferably at least one selected from the group consisting of synthetic resin fine particles and inorganic fine particles. That is, as the fine particles, either synthetic resin fine particles or inorganic fine particles may be used, or a mixture of both may be used.
Synthetic resin fine particles include silicone resin fine particles, styrene resin fine particles, olefin resin fine particles (for example, polyethylene fine particles, polypropylene fine particles), polyvinyl acetate fine particles, polyester fine particles, polyamide fine particles, polymethacrylate fine particles, fluororesin fine particles. It is preferably at least one selected from the group consisting of Further, as the fine particles, only one kind of the above-mentioned synthetic resin fine particles may be used, and fine particles of different materials may be mixed and used.

The inorganic fine particles are preferably at least one selected from the group consisting of ceramic fine particles, talc fine particles, and metal oxide fine particles. The ceramic fine particles are preferably at least one selected from the group consisting of silica fine particles, alumina fine particles, zirconia fine particles, and zeolite fine particles. The metal oxide fine particles are preferably at least one selected from the group consisting of titanium oxide fine particles and zinc oxide fine particles. As the fine particles, only one kind of the above inorganic fine particles may be used, or different fine particles may be mixed and used.
And as a magnitude | size of microparticles | fine-particles, 0.5-10 micrometers, Preferably, 2-8 micrometers is preferable. The average particle diameter of the fine particles relative to the average film thickness of the coating layer 3 (average film thickness including fine particles) is preferably 0.2 to 1.5 times, and more preferably 0.3 to 1. 2 times, particularly preferably 0.4 to 1.0 times. If it is 1.5 times or less, there is no decrease in airtightness due to the rough surface, and if it is 0.2 times or more, sufficient roughening can be achieved.
In addition, the fine particles preferably have adhesiveness to the film, but may not be adhesive and may be retained by the film. The addition amount of the fine particles is preferably about 70 to 90% of the weight of the coating layer (weight after solidification of the coating layer) and 50 to 70% in the volume ratio.
By having the coating layer 3 as described above, the gasket 1 of the present invention has a stable slidability without applying a lubricant to the sliding surface, and maintains the sealing performance in the medicine storage space. Can do. Moreover, the coating layer 3 has a roughened surface as shown in FIG. 11 by containing fine particles.

Next, a method for forming the coating layer 3 will be described.
The coating layer is formed by adjusting a coating solution obtained by dispersing and suspending the above-mentioned fluorine-based resin, silicon-based resin, urethane-based resin and fine particles appropriately mixed with purified water. Further, a coating solution containing the coating solution as a main component and an auxiliary agent for enhancing adhesion to a substrate containing a silane coupling agent, that is, an anti-release agent (which also functions as a curing agent) is added. It is good. In particular, the auxiliary agent containing a silane coupling agent also functions as a curing agent.
As the silane coupling agent, an acrylic (methacrylic) functional silane coupling agent, an epoxy functional silane coupling agent, an amino (imino) functional silane coupling agent, and the like can be used.
Specific examples of the acrylic (methacrylic) functional silane coupling agent include 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropyltriethoxysilane, 3-acryloxypropyltrimethoxysilane, and 3-acryloxypropyltriethoxy. Examples include silane, methacryloxymethyltrimethoxysilane, methacryloxymethyltriethoxysilane, acryloxymethyltrimethoxysilane, and acryloxymethyltriethoxysilane.
Specific examples of the epoxy functional silane coupling agent include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 2- (3,4-epoxycyclohexyl) ethyltriethoxysilane and the like.

Specific examples of the amino (imino) functional silane coupling agent include H ₂ NCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (OCH ₃ ) ₃ , H ₂ NCH ₂ CH ₂ NHCH ₂ CH ₂ CH ₂ Si (CH ₃ ) (OCH ₃ ) ₂ , (C ₂ H ₅ O) ₃ Si (CH ₂ ) ₃ NH (CH ₂ ) ₂ NH (CH ₂ ) ₃ Si (OC ₂ H ₅ ) ₃ amino group and / or imino group-containing alkoxysilane, the amino group and / or imino group-containing alkoxysilane, and CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si Examples thereof include reaction products with methacryloxysilane compounds such as (OCH ₃ ) ₃ , CH ₂ ═C (CH ₃ ) COOCH ₂ CH ₂ CH ₂ Si (OCH ₂ CH ₂ OCH ₃ ) ₃ .
The ratio of the silane coupling agent to the main agent in the case of adding the silane coupling agent is preferably 100 (main agent): 1 to 20, particularly preferably 100 (main agent): 3 to 10.
Moreover, it is preferable that the addition amount of the microparticles | fine-particles mentioned above is 10-30 weight% with respect to the coating liquid or the said main ingredient, Furthermore, 15-20 weight%.

And a coating layer is obtained by making it harden | cure, after apply | coating the coating liquid with respect to the clean gasket surface. At this time, as a method of applying to the gasket surface, a conventionally known method such as dipping or spraying can be used. In particular, it is preferable to spray coat (spray coat) the coating solution in a state where the coated object is rotated (specifically, 100 to 600 rpm). Furthermore, when performing spray application, it is preferable to perform after heat-processing the coating | coated object site | part of a gasket to about 90-110 degreeC. By doing in this way, since it fixes quickly with respect to the surface to be coated, handling is easy.
Further, as a curing method, it may be left at room temperature, but heat curing is preferable. The method of thermosetting is not particularly limited as long as it is a method that does not alter or deform the gasket base material, but conventionally known methods such as hot air drying, a drying oven using infrared rays, or a method using a vacuum dryer. Can be done by the method. If the coating solution contains a silane coupling agent, the effect is achieved in a short time. In forming such a coating layer, the coating layer is formed by appropriately controlling the concentration of the mixed solution, the dipping method, or the spraying method.

In addition, additives such as surfactants, alcohols, emulsification aids, hydrophilic organic solvents, etc. may be used for the preparation of coating liquids containing fluororesins, silicon resins and urethane resins and fine particles. .
The surfactant is preferably a nonionic surfactant. Any nonionic surfactant may be used, but polyoxyethylene alkylphenyl ethers having an alkyl group such as octyl, nonyl, dodecyl, etc. Oxyethylene alkyl ethers, polyethylene glycol oleic acid monoester, stearic acid monoester, stearic acid diester, polyethylene glycol fatty acid esters such as lauric acid monoester, polyoxyethylene alkyl having alkyl group such as lauryl, stearyl, oleyl Amines, polyoxyethylene sorbitan monolaurate, polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate Ter, polyoxyethylene sorbitan tristearate, polyoxyethylene sorbitan monooleate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as coconut oil fatty acid polyoxyethylene sorbitan, polyethylene glycol ethers , Fatty acid diethanolamides such as lauric acid diethanolamide, sucrose fatty acid esters, fatty acid monoglycerides such as lauric acid monoglyceride, stearic acid monoglyceride, oleic acid monoglyceride, sorbitan monolauric acid ester, sorbitan monopalmitic acid ester, sorbitan monostearic acid ester , Sorbitan distearate, sorbitan tristearate Sorbitan fatty acid esters such as sorbitan monooleate, sorbitan trioleate, polyoxyethylene fatty acid amides such as polyoxyethylene lauric acid amide, polyoxyethylene stearic acid amide, polyoxyethylene oleic acid amide, polyoxyethylene Castor oil, polyoxyethylene hydrogenated castor oil, and the like can be used.
As the emulsification aid, N-methylpyrrolidone is preferable, and as the hydrophilic organic solvent, i-propanol, butyl carbitol, methyl ethyl ketone and the like are used.

Moreover, as shown in FIG. 5, the syringe 10 which is an embodiment of the medical device of the present invention has an injection needle mounting portion 15 provided at the front end portion and a syringe outer portion provided with a flange 16 facing the rear end portion. A cylinder 11, a syringe gasket 1 capable of sliding in a liquid-tight and air-tight manner on an inner surface 12 of the syringe outer cylinder 11, a plunger 17 attached to or attachable to the syringe gasket 1, and a syringe outer cylinder 11 A sealing member 18 that seals the injection needle mounting portion 15, and a medicine storage that stores a medicine 26 formed between the sealing member 18, the outer cylinder inner surface 12 (and the inner surface of the coating layer 13), and the syringe gasket 1. It consists of part 19. The injection needle attachment portion 15 may be attached with an injection needle instead of the sealing member 18. Moreover, as a sealing member, as shown in FIG. 5, the type which can insert a double-headed needle directly is preferable.
In particular, the medical device is a prefilled syringe 25, and includes a syringe 10 and a drug 26 as shown in FIG.

The outer cylinder 11 for a syringe is a cylindrical member in which an injection needle attachment portion 15 is provided at a front end portion and a flange portion 16 is provided at a rear end portion. The syringe outer cylinder 11 is made of a transparent or translucent material. Preferably, it is made of a material having low oxygen permeability and water vapor permeability. Further, the forming material is preferably a material having a glass transition point of 110 ° C. or higher or a melting point.
Examples of the material for forming the outer cylinder 11 include polyolefins such as polypropylene, polyethylene, poly (4-methylpentene-1) and cyclic polyolefin, polyesters such as polyethylene terephthalate, polyethylene naphthalate, and amorphous polyarate, polystyrene, polyamide, Polycarbonate, polyvinyl chloride, acrylic resin, acrylonitrile-butadiene-styrene copolymer, amorphous polyetherimide and the like are preferable, and in particular, polypropylene, poly (4-methylpentene-1), cyclic polyolefin, polyethylene naphthalate, and Amorphous polyetherimide is preferred in terms of transparency and high-pressure steam sterilization resistance. These resins are not limited to the outer cylinder and can be used in common for containers that can store medicines.

Moreover, in the syringe of the Example of this invention, the gasket 1 for syringes provided with the coating layer 3 mentioned above is used. The gasket 1 for a syringe provided with the coating layer 3 is as described above.
As shown in FIG. 5, the plunger 17 includes a main body portion 20 extending in the axial direction having a cross-shaped cross section, and a plunger-side screwing portion provided at a distal end portion of the plunger 17 screwed with the plunger mounting portion 4. 21, a pressing disk portion 22 provided at the rear end of the main body portion 20, and a rib provided in the middle of the main body portion 20.
And the medicine 26 is accommodated in the inside of the syringe 10 of this embodiment. Examples of the drug 26 include poorly water-soluble, highly adsorbable chemicals, low-viscosity and high-permeability chemicals containing surfactants, electrolytes, electrolytes, vitamins, minerals, antibiotics, and the like, Powdered or freeze-dried drugs or solutions such as protein preparations are used.
And as a constituent material of the plunger 17 and the sealing member 18, it is preferable to use hard or semi-rigid resin, such as a high density polyethylene, a polypropylene, a polystyrene, a polyethylene terephthalate.

  The medical device of the present invention is not limited to a syringe, as long as it is a medical device including a first medical member and a second medical member that slidably contacts the first medical member. It may be a medical device. For example, it may be a vial with a rubber stopper, an infusion bag, a blood collection tube, a reduced pressure blood collection tube, or the like. In addition, the medical device of the present invention is not limited to a syringe gasket, and may be any medical device such as an O-ring, a stopper, and a lid as long as it can slidably contact a medical member. For example, it may be a rubber stopper for a vial, a lid for an infusion bag, or the like.

Next, as for the syringe 30 which is another Example of the medical device of this invention, FIG. 6 applies the medical device of the Example of this invention to a syringe.
As shown in FIG. 6, the syringe 30 of this embodiment includes a syringe outer cylinder 41 provided with an injection needle mounting portion 15 at the front end portion and a flange 16 facing the rear end portion, and an outer cylinder for syringe. Seal the syringe gasket 31 that can be slid liquid-tight and air-tightly on the inner surface 42 of the 41, the plunger 17 that is attached to or attachable to the syringe gasket 31, and the injection needle mounting portion 15 of the syringe outer cylinder 41. A sealing member 18, and a medicine storage portion 19 that stores the medicine 26 formed between the sealing member 18, the outer cylinder inner surface 42, and the syringe gasket 31. The injection needle attachment portion 15 may be attached with an injection needle instead of the sealing member 18. Moreover, as a sealing member, as shown in FIG. 6, the type which can insert a double-headed needle directly is preferable.

The syringe outer cylinder 41 is a cylindrical member in which the injection needle attachment portion 15 is provided at the front end portion and the flange portion 16 is provided at the rear end portion. The syringe outer cylinder 41 is formed of a transparent or translucent material, preferably a material having low oxygen permeability and water vapor permeability. The syringe outer cylinder 41 is formed of a material having oxygen permeability and low water vapor permeability when packaged in a gas barrier envelope together with an oxygen scavenger. Further, the forming material is preferably a material having a glass transition point of 110 ° C. or higher or a melting point.
Examples of the material for forming the outer cylinder 41 include polyolefins such as polypropylene, polyethylene, poly (4-methylpentene-1) and cyclic polyolefin, polyesters such as polyethylene terephthalate, polyethylene naphthalate, and amorphous polyarate, polystyrene, polyamide, Polycarbonate, polyvinyl chloride, acrylic resin, acrylonitrile-butadiene-styrene copolymer, amorphous polyetherimide and the like are preferable, and in particular, polypropylene, poly (4-methylpentene-1), cyclic polyolefin, polyethylene naphthalate, and Amorphous polyetherimide is preferred in terms of transparency and high-pressure steam sterilization resistance. These resins are not limited to the outer cylinder and can be used in common for containers that can store medicines.

  Moreover, in the Example of this invention, the well-known thing can be used as the gasket 31 for syringes. The constituent material of the syringe gasket 31 is preferably an elastic material. Elastic materials include natural rubber, isoprene rubber, butyl rubber, chloroprene rubber, nitrile-butadiene rubber, styrene-butadiene rubber, silicone rubber and other rubber materials (especially those vulcanized), styrene elastomers, hydrogenated Styrenic elastomers, and these styrenic elastomers mixed with polyolefins such as polyethylene, polypropylene, polybutene, and α-olefin copolymers, and oils such as liquid paraffin and process oil, and inorganic powders such as talc, cast, and mica Is mentioned. Furthermore, polyvinyl chloride elastomers, olefin elastomers, polyester elastomers, polyamide elastomers, polyurethane elastomers, and mixtures thereof can be used as constituent materials. As the constituent material, butyl rubber, diene rubber, and styrene elastomer are particularly preferable from the viewpoints of elastic properties, high-pressure steam sterilization resistance, and the like.

As shown in FIG. 5, the plunger 17 includes a main body portion 20 extending in the axial direction having a cross-shaped cross section, and a plunger-side screwing portion provided at a distal end portion of the plunger 17 screwed with the plunger mounting portion 4. 21, a pressing disk portion 22 provided at the rear end of the main body portion 20, and a rib provided in the middle of the main body portion 20.
Examples of the drug 26 include poorly water-soluble and highly adsorptive chemicals, low-viscosity and high-permeability chemicals containing surfactants, electrolytic chemicals, vitamins, minerals, antibiotics, and other chemicals. In addition, powdered or freeze-dried drugs or solutions such as protein preparations are used.
And as a constituent material of the plunger 17 and the sealing member 18, it is preferable to use hard or semi-rigid resin, such as a high density polyethylene, a polypropylene, a polystyrene, a polyethylene terephthalate.

Moreover, you may use the gasket 1 for syringes provided with the coating layer 3 mentioned above instead of the gasket 31. FIG. The gasket 1 for a syringe provided with the coating layer 3 is as described above.
In addition, the medical device of the present invention is any medical device as long as the medical device includes the first medical member and the second medical member that slidably contacts the first medical member. May be. For example, it may be a vial with a rubber stopper, an infusion bag, a blood collection tube, a reduced pressure blood collection tube, or the like. The contact after the first medical member and the second medical member is preferably liquid-tight. The medical device of the present invention may be a rubber stopper of a vial, a lid material of an infusion bag, or the like. Moreover, as long as the 1st medical member contacts a 2nd medical member slidably, not only a gasket for syringes but any medical devices, such as an O-ring-shaped thing, a plug body, and a cover body It may be.

Hereinafter, specific examples of the present invention will be described.
Example 1
The core part of the gasket for syringes of the shape shown in FIG. 1 and FIG. 2 was produced using butyl rubber. The core portion was formed by press molding a vulcanizable rubber composition in which an additive was added to butyl rubber. The shape of the obtained core part is 20 mm in length, 23.7 mm in outer diameter at the front and rear end side annular rib portions, 10 mm in length between the front end side annular rib center and the rear end side annular rib center, and the front end side The outer diameter is 21.5 mm at the same outer diameter portion between the annular rib and the rear end side annular rib, the length (depth) of the recessed portion for mounting the plunger having an internal thread portion is 8 mm, the distal end side of the recessed portion for mounting the plunger And an inner diameter of 15 mm at the rear end side.
Next, 100 parts by weight of purified water, 1 part by weight of a fluorine-based resin, 10 parts by weight of a silicon-based resin, 3 parts by weight of a urethane-based resin, 20 parts by weight of talc fine particles (average particle size of about 3 μm), 1 part by weight of N-methylpyrrolidone Parts, 1 part by weight of butyl carbitol, and 1 part by weight of polyoxyethylene alkyl ether were added to prepare a base agent for the coating solution. In addition, as a fluororesin, polyfluorone (trademark) TFE (made by Daikin Industries Ltd.) which has tetrafluoroethylene as a main component was used. As the silicon resin, SE1980 (manufactured by Toray Dow Corning Silicone Co., Ltd.), which is an aqueous silicon resin (aqueous silicone compound), was used. As the urethane resin, Lausanne 1100 (manufactured by Toyo Polymer Co., Ltd.), which is an aqueous urethane resin, was used.
Furthermore, as a silane coupling agent, TSL8310 (made by Toshiba GE Silicon Co., Ltd.) which has vinyltrimethoxysilane as a main component was prepared.
Then, 5 parts by weight of a silane coupling agent was added to 95 parts by weight of the main agent and mixed to prepare a coating solution.
Then, under the environment of room temperature and normal pressure, the gasket core member produced as described above is rotated (300 rpm) around its central axis as shown in FIG. After the application liquid was spray-coated, the syringe gasket of the present invention was produced by drying at 140 ° C. for 30 minutes. In addition, the average thickness of the coating layer formed on the surface of the core member was about 5 μm, and the particle diameter of the fine particles with respect to the average film thickness of the coating layer was 0.6 times.

(Example 2)
A syringe gasket of the example was produced in the same manner as in Example 1 except that the amount of talc fine particles (average particle size 5 μm) added to the main agent of Example 1 was changed to 5 parts by weight. In addition, the average thickness of the coating layer formed on the surface of the core member was about 6 μm. This gasket was designated as Example 2.

(Example 3)
A syringe gasket of the example was produced in the same manner as in Example 1 except that the amount of talc fine particles (average particle size 5 μm) added to the main agent of Example 1 was 10 parts by weight. In addition, the average thickness of the coating layer formed on the surface of the core member was about 6 μm. This gasket was referred to as Example 3.

Example 4
A syringe gasket of the example was manufactured in the same manner as in the example 1 except that the amount of the talc fine particles (average particle diameter 5 μm) added to the main agent of the example 1 was 15 parts by weight. In addition, the average thickness of the coating layer formed on the surface of the core member was about 6 μm. This gasket was referred to as Example 4.

(Example 5)
A syringe gasket of the example was produced in the same manner as in the example 1 except that the amount of the talc fine particles (average particle size 5 μm) added to the main agent of the example 1 was 25 parts by weight. The average thickness of the coating layer formed on the surface of the core member was about 6 μm (this gasket was referred to as Example 5).

(Example 6)
A syringe gasket of the example was produced in the same manner as in Example 1 except that the amount of talc fine particles (average particle size 5 μm) added to the main agent of Example 1 was 30 parts by weight. In addition, the average thickness of the coating layer formed on the surface of the core member was about 7 μm. This gasket was referred to as Example 6.

(Comparative Example 1)
A coating solution was prepared by adding 1 part by weight of a fluorine-based resin and 3 parts by weight of a urethane-based resin to 100 parts by weight of purified water. Others were the same as in Example 1, and a syringe gasket for a comparative example was produced. In addition, the average thickness of the coating layer formed on the surface of the core member was about 5 μm. This gasket was referred to as Comparative Example 1.

(Comparative Example 2)
A coating solution was prepared by adding 10 parts by weight of a silicon-based resin and 3 parts by weight of a urethane-based resin to 100 parts by weight of purified water. Others were the same as in Example 1, and a syringe gasket for a comparative example was produced. In addition, the average thickness of the coating layer formed on the surface of the core member was about 5 μm. This gasket was referred to as Comparative Example 2.

(Comparative Example 3)
100 parts by weight of purified water, 1 part by weight of fluorine resin, 10 parts by weight of silicon resin, 3 parts by weight of urethane resin, 1 part by weight of N-methylpyrrolidone, 1 part by weight of butyl carbitol, 1 part by weight of polyoxyethylene alkyl ether The main component of the coating liquid was adjusted by adding parts. Then, 5 parts by weight of a silane coupling agent was added to 95 parts by weight of the main agent and mixed to prepare a coating solution. Others were the same as in Example 1, and a syringe gasket for a comparative example was produced. In addition, the average thickness of the coating layer formed on the surface of the core member was about 7 μm. This gasket was referred to as Comparative Example 3.

(Comparative Example 4)
A butyl rubber gasket produced in the same manner as in Example 1 except that no coating layer was provided was used as Comparative Example 4.

(Comparative Example 5)
A commercially available syringe (manufactured by Terumo Corporation, 30 ml) using a gasket made of SEBS thermoplastic elastomer was used as Comparative Example 5.

(Comparative Example 6)
The coating liquid and gasket core member prepared in Example 1 were used. Under normal temperature and normal pressure, after immersing the gasket core member in the coating solution for 1 second, immediately lift it up, confirm that there is no dripping, put it in a 150 ° C. oven, and dry it for 30 minutes. A gasket for a syringe was produced. In addition, the average thickness of the coating layer formed on the surface of the core member was about 8 μm. This gasket was designated as Comparative Example 6.

(Experiment)
A syringe outer cylinder having the shape shown in FIG. 5 was produced by injection molding using polypropylene [manufactured by Nippon Polychem Co., Ltd.] as a forming material of the outer cylinder for syringe. The inner diameter of the cylindrical portion of the syringe outer cylinder was 23.5 mm, and the length was 95 mm. Moreover, the plunger of the shape shown in FIG. 5 was produced by injection molding using polypropylene (manufactured by Nippon Polychem Co., Ltd.) as a plunger forming material.
And the gasket for syringes of each Example and each comparative example and said plunger were assembled in said outer cylinder for syringes, and several syringes were produced. In Comparative Examples 4 and 5, silicone oil is applied to the inner surface of the outer cylinder in advance. And each said syringe performed the following evaluation, after performing the autoclave sterilization process except the comparative example 5. FIG.

(Experiment 1: sliding resistance measurement test)
The sliding resistance value of each syringe was measured by an autograph (AGS1kNG, manufactured by Shimadzu Corporation) using an experimental apparatus as shown in FIG. Specifically, the tip of the syringe and the rear end of the plunger are fixed to the measurement object fixing part of the autograph, and the initial sliding resistance value (maximum sliding resistance) when the plunger is lowered by 30 mm at a speed of 100 mm / min. Dynamic resistance value: maximum stress kgf required in the 0 to 30 mm section) and average sliding resistance value (average sliding resistance value kgf in the 25 to 50 mm section) were measured, and the results shown in Table 1 of FIG. became.
As shown in Table 1, the syringes using the gaskets of Examples 1 to 5 are smaller in both the initial sliding resistance value and the average sliding resistance value than the syringes using the gaskets of Comparative Examples 1 to 6. there were. In addition, since there is little difference between the initial sliding resistance value and the average sliding resistance value, there is almost no risk of the chemical solution popping out when the plunger is started, and the chemical solution can be discharged safely and simply. On the other hand, in Comparative Example 4 and Comparative Example 5, the average sliding resistance value is at an acceptable level, but the difference from the initial sliding resistance value is very large, suggesting the above-mentioned danger. In Comparative Examples 2 and 3, the difference between the maximum sliding resistance value and the average sliding resistance value is not large, but the sliding resistance value is large, and the force pushing the plunger becomes heavier than necessary. Is inferior in operability and convenience.
On the other hand, in Comparative Example 6, as a result of changing the coating method on the gasket surface, a decrease in the surface roughness was confirmed, and along with this, an increase in the initial sliding resistance value was also confirmed. From this, it was confirmed that the spraying method is more preferable in order to effectively improve the surface roughness due to the added talc.
In Examples 1 to 4, when the amount of talc added was changed, the sliding resistance value clearly decreased in inverse proportion to the amount of talc added. That is, it is suggested that the effect of the coating agent is improved by adding talc to the rough surface properties.

(Experiment 1.5: Pressure test specified in the standard of disposable syringes)
The pressure test prescribed in the pressure test in the medical device equipment standard “Disposable syringe standard” Ministry of Health and Welfare Notification No. 442 (December 28, 1971) was conducted. The results are shown in Table 1 in FIG.

(Experiment 2: Sealing test with a highly permeable reagent)
Usually, sealability evaluation was performed using an AGELESS (registered trademark) checker (manufactured by Mitsubishi Gas Chemical Co., Ltd.), which is sold as a reagent used for a sealability test of a heat seal part such as a plastic soft packaging material. Specifically, about 5 mL of ageless checker is put in a syringe outer cylinder whose tip 15 is sealed with a cap 18, and 5 pieces each including each gasket including the embodiment are prepared, and the plunger side With the pressure of 2.5 kgf / cm ² applied, leave the syringe upright with the plunger side down and let it stand in a 60 ° C. constant temperature bath for 3 weeks to prevent liquid leakage from the gasket sliding part. When visually confirmed, the results shown in Table 1 were obtained.

(Experiment 3)
The surface roughness of the gasket of Example 1 and the gasket of Comparative Example 6 was measured. The measuring method was performed according to JISB0601 (1994). The results were as shown in Table 2 shown in FIG.

(Experiment 4)
The surface state and cross-sectional state of the gasket of Example 1 and the gasket of Comparative Example 6 were observed with a laser microscope.
FIG. 11 is a surface state diagram obtained by photographing the surface of the gasket of Example 1 with a laser microscope. FIG. 12 shows a cross-sectional state diagram obtained by photographing a cross section of the gasket of Example 1 with a laser microscope. FIG. 13 shows a three-dimensional state diagram created from data obtained by photographing the gasket of Example 1 with a laser microscope. Also from these, it was confirmed that the gasket of Example 1 had considerable unevenness on the surface.
FIG. 14 is a surface state diagram obtained by photographing the surface of the gasket of Comparative Example 6 with a laser microscope. FIG. 15 shows a cross-sectional state diagram obtained by photographing a cross section of the gasket of Comparative Example 6 with a laser microscope. FIG. 16 shows a three-dimensional state diagram created from data obtained by photographing the gasket of Comparative Example 6 with a laser microscope. Also from these, it was confirmed that the surface of the gasket of Comparative Example 6 was considerably smoother than the gasket of Example 1.
Further, Example 2 and Comparative Example 6 have the same surface roughness Ra, but Comparative Example 6 produced by the dipping method does not have a rough surface as shown in FIGS. As a result, both the initial sliding value and the difference between the initial sliding value and the average sliding value are greatly different.

FIG. 1 is a front view of a syringe gasket according to an embodiment of the present invention. 2 is a cross-sectional view of the syringe gasket shown in FIG. FIG. 3 is a plan view of the syringe gasket shown in FIG. 1. FIG. 4 is a bottom view of the syringe gasket shown in FIG. 1. FIG. 5 is a cross-sectional view of a prefilled syringe that is an embodiment of the present invention. FIG. 6 is a cross-sectional view of a prefilled syringe that is another embodiment of the present invention. FIG. 7 is an explanatory diagram for explaining a method of applying a coating liquid to a syringe gasket that is a coating target. FIG. 8 is an explanatory diagram of an experimental apparatus used for measuring the discharge characteristic results of the syringe gasket and the prefilled syringe according to the embodiment of the present invention. FIG. 9 is a table 1 showing experimental results of the gaskets of the examples of the present invention and the gaskets of the comparative examples. FIG. 10 is a table 2 showing experimental results of the gaskets of the examples of the present invention and the gaskets of the comparative examples. FIG. 11 is a surface state diagram obtained by photographing the surface of the gasket of Example 1 with a laser microscope. FIG. 12 is a cross-sectional state diagram obtained by photographing a cross section of the gasket of Example 1 with a laser microscope. FIG. 13 is a three-dimensional state diagram created from data obtained by photographing the gasket of Example 1 with a laser microscope. FIG. 14 is a surface state diagram obtained by photographing the surface of the gasket of Comparative Example 6 with a laser microscope. FIG. 15 is a cross-sectional state diagram obtained by photographing a cross section of the gasket of Comparative Example 6 with a laser microscope. FIG. 16 is a three-dimensional state diagram created from data obtained by photographing the gasket of Comparative Example 6 with a laser microscope.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 Gasket for syringes 2 Core part 3 Coating layer 10 Medical tool 12 Inner surface 26 Drug

Claims (30)

A medical device that is slidably in contact with a medical member, the medical device including a coating layer provided on a portion that contacts the medical member, the coating layer including a slidability-imparting component and a flexible material. A coating film formed from a composition containing a property-imparting component and fine particles held in the coating film, and the coating layer has a rough surface caused by the fine particles. Medical equipment. The medical device according to claim 1, wherein the slidability imparting component is a fluorine-based resin and a silicon-based resin. The medical device according to claim 1 or 2, wherein the flexibility-imparting component is a urethane-based resin. A medical device that is slidably in contact with a medical member, the medical device including a coating layer provided in a portion in contact with the medical member, wherein the coating layer includes a fluorine-based resin and a silicon-based resin. And a coating film formed of a composition containing a urethane resin and fine particles held in the coating film, and the coating layer has a rough surface caused by the fine particles. Medical equipment. The medical device according to any one of claims 1 to 4, wherein the medical device is made of an elastic material. The medical device according to any one of claims 1 to 4, wherein the medical device is slidably housed inside a medical member. The medical device according to claim 6, wherein the medical member is a syringe outer cylinder, and the medical device is a syringe gasket. The medical device according to claim 7, wherein the coating layer also covers an outer surface portion of the syringe gasket that defines a space together with an inner surface of the syringe outer cylinder. The medical device according to any one of claims 1 to 8, wherein the coating layer covers only a portion of the medical device that comes into contact with the medical member. A medical device comprising a first medical member and a second medical member slidably in contact with the first medical member, wherein the first medical member is the second medical member. A coating layer provided on a portion in contact with the medical member, the coating layer comprising a coating formed of a composition containing a slidability imparting component and a flexibility imparting component, and fine particles held in the coating; The medical device is characterized in that the coating layer has a rough surface caused by the fine particles. The medical device according to claim 10, wherein the slidability imparting component is a fluorine-based resin and a silicon-based resin. The medical device according to claim 10 or 11, wherein the flexibility-imparting component is a urethane-based resin. A medical device comprising a first medical member and a second medical member slidably in contact with the first medical member, wherein the first medical member is the second medical member. A coating layer provided on a portion in contact with the medical member, the coating layer comprising a coating formed of a composition containing a fluorine-based resin, a silicon-based resin, and a urethane-based resin, and fine particles held in the coating And the coating layer has a rough surface caused by the fine particles. The medical device according to claim 10, wherein the first medical member is made of an elastic material. The medical device according to any one of claims 10 to 14, wherein the first medical member is slidably housed inside the second medical member. The medical device according to claim 15, wherein the medical device is a syringe, the first medical member is a gasket, and the second medical member is an outer cylinder. The medical device according to claim 16, wherein the medical device is a prefilled syringe. The medical device according to any one of claims 10 to 17, wherein the covering layer covers only a portion of the first medical member that comes into contact with the second medical member. The medical device according to any one of claims 2 to 9 or 11 to 18, wherein the urethane-based resin, silicon-based resin, or a mixture thereof constituting the coating layer functions as a binder. The medical device according to claim 2, wherein at least one of the fluororesin, the silicon resin, and the urethane resin is a thermosetting resin. 21. The medical device according to claim 2, wherein the fluororesin has polytetrafluoroethylene or polytetrafluoroethylene as a basic structure. The medical device according to any one of claims 2 to 9 or 11 to 21, wherein the silicon-based resin has polysiloxane in a basic structure. The medical device according to any one of claims 3 to 9, or 12 to 22, wherein the urethane-based resin has polyurethane as a basic structure. The medical device according to any one of claims 1 to 23, wherein the coating layer has a thickness of 1 to 20 µm. The medical device according to any one of claims 1 to 24, wherein the composition forming the film contains a cured product of a silane coupling agent. The medical device according to any one of claims 1 to 25, wherein the fine particles are at least one selected from the group consisting of synthetic resin fine particles and inorganic fine particles. The synthetic resin fine particles are at least one selected from the group consisting of silicone resin fine particles, styrene resin fine particles, olefin resin fine particles, polyvinyl acetate fine particles, polyester fine particles, polyamide fine particles, polymethacrylate fine particles, and fluororesin fine particles. The medical device according to claim 26. 27. The medical device according to claim 26, wherein the inorganic fine particles are at least one selected from the group consisting of ceramic fine particles, talc fine particles, and metal oxide fine particles. 29. The medical device according to claim 28, wherein the ceramic fine particles are at least one selected from the group consisting of silica fine particles, alumina fine particles, zirconia fine particles, and zeolite fine particles. 29. The medical device according to claim 28, wherein the metal oxide fine particles are at least one selected from the group consisting of titanium oxide fine particles and zinc oxide fine particles.